WO2018199720A1 - Dispositif de modulation optique - Google Patents

Dispositif de modulation optique Download PDF

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Publication number
WO2018199720A1
WO2018199720A1 PCT/KR2018/005021 KR2018005021W WO2018199720A1 WO 2018199720 A1 WO2018199720 A1 WO 2018199720A1 KR 2018005021 W KR2018005021 W KR 2018005021W WO 2018199720 A1 WO2018199720 A1 WO 2018199720A1
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WO
WIPO (PCT)
Prior art keywords
layer
polymer film
degrees
modulation device
optical modulation
Prior art date
Application number
PCT/KR2018/005021
Other languages
English (en)
Korean (ko)
Inventor
임은정
김남훈
유정선
김진홍
이현준
김민준
홍경기
문인주
오동현
Original Assignee
주식회사 엘지화학
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Filing date
Publication date
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to JP2019556618A priority Critical patent/JP7013630B2/ja
Priority to EP18792339.6A priority patent/EP3617786B1/fr
Priority to US16/500,248 priority patent/US11347080B2/en
Priority to CN201880027094.8A priority patent/CN110546553B/zh
Publication of WO2018199720A1 publication Critical patent/WO2018199720A1/fr
Priority to JP2021164353A priority patent/JP7225508B2/ja

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    • G02F1/01Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
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    • G02F1/1326Liquid crystal optical waveguides or liquid crystal cells specially adapted for gating or modulating between optical waveguides
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    • G02F1/13Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
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    • G02F1/00Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
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    • G02F1/13Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
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    • G02F1/13Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333Constructional arrangements; Manufacturing methods
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    • G02F1/133635Multifunctional compensators
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    • G02FOPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333Constructional arrangements; Manufacturing methods
    • G02F1/1343Electrodes
    • G02F1/13439Electrodes characterised by their electrical, optical, physical properties; materials therefor; method of making
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333Constructional arrangements; Manufacturing methods
    • G02F1/1347Arrangement of liquid crystal layers or cells in which the final condition of one light beam is achieved by the addition of the effects of two or more layers or cells
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F2202/00Materials and properties
    • G02F2202/04Materials and properties dye
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F2413/00Indexing scheme related to G02F1/13363, i.e. to birefringent elements, e.g. for optical compensation, characterised by the number, position, orientation or value of the compensation plates
    • G02F2413/01Number of plates being 1

Definitions

  • the present application relates to a light modulation device.
  • An optical modulation device in which an optical modulation layer containing a liquid crystal compound or the like is positioned between two opposing substrates is used for various applications.
  • Patent Document 1 European Patent Publication No. 00223111 discloses a so-called GH cell (Guest host cell) to which a mixture of a liquid crystal host material and a dichroic dye guest is applied.
  • permeability apparatus used as a modulation layer is known.
  • a glass substrate having excellent optical isotropy and good dimensional stability has been mainly used as the substrate.
  • optical modulation device is not limited to the display device, but is expanded to smart windows such as eyewear and sunroof, and the shape of the device is not limited to a flat surface, and various designs such as folding shapes are applied.
  • shape of the device is not limited to a flat surface, and various designs such as folding shapes are applied.
  • polymer film substrate instead of a glass substrate as a substrate of the optical modulation device while also showing the necessity of a flexible device.
  • the present application is directed to a light modulation device.
  • an optical and mechanically anisotropic polymer film is applied to a substrate, and an object of the present invention is to provide an optical modulation device having excellent mechanical and optical properties.
  • Vertical, parallel, orthogonal or horizontal, etc. of the terms defining the angle in the present specification means a substantially vertical, parallel, orthogonal or horizontal in a range that does not impair the desired effect, the range of the vertical, parallel, orthogonal or horizontal Includes errors such as manufacturing error or variation.
  • each of the above cases may include an error within about ⁇ 15 degrees, an error within about ⁇ 10 degrees or an error within about ⁇ 5 degrees.
  • the physical properties mentioned in the present specification unless the measurement temperature affects the corresponding physical properties, the physical properties are measured at room temperature unless otherwise specified.
  • room temperature is a temperature in a particularly warmed or undecreased state, and any temperature within a range of about 10 ° C to 30 ° C, for example, about 15 ° C or more, 18 ° C or more, 20 ° C or more, or about 23 ° C. It may mean a temperature of about 27 ° C. or lower while being higher than or equal to ° C.
  • the unit of temperature referred to in this specification is ° C.
  • the retardation and refractive index referred to herein mean the refractive index for light of about 550 nm wavelength unless otherwise specified.
  • an angle formed by any two directions mentioned herein may be an acute angle of an acute or obtuse angle formed by the two directions, or may be a small angle among angles measured in a clockwise and counterclockwise direction. . Therefore, unless otherwise specified, the angles referred to herein are positive. However, in order to indicate the measurement direction between the angles measured in the clockwise or counterclockwise direction, one of the angles measured in the clockwise direction and the angle measured in the counterclockwise direction is expressed as a positive number, and the other The angle of can also be represented as a negative number.
  • liquid crystal compound included in the active liquid crystal layer or the light modulation layer herein may be referred to as liquid crystal molecules, liquid crystal host (when included with the dichroic dye guest), or simply liquid crystal.
  • the present invention relates to a light modulation device of the present application.
  • the term light modulation device may refer to a device capable of switching between states of at least two or more different lights.
  • the state of other light may mean a state in which at least the transmittance and / or the reflectance are different.
  • Examples of states that the light modulation device can implement include transmission, blocking, high reflection and / or low reflection mode states.
  • the light modulation device may be a device capable of switching at least between the transmission and blocking mode states, or a device capable of switching between the high reflection and low reflection mode states.
  • the transmittance of the optical modulator in the transmission mode is at least 20%, at least 25%, at least 30%, at least 35%, at least 40%, at least 45%, at least 50%, at least 55%, at least 60%, 65 At least%, at least 70%, at least 75% or at least 80%.
  • the transmittance of the optical modulator in the blocking mode is 60% or less, 55% or less, 50% or less, 45% or less, 40% or less, 35% or less, 30% or less, 25% or less, 20% or less, 15 Up to 10% or up to 5%.
  • the upper limit of the transmittance of may be about 100%, and the lower limit of the transmittance in the blocking mode state may be about 0%.
  • the difference between the transmittance in the transmission mode state and the transmittance in the blocking mode state (transmission mode-blocking mode) in the optical modulation device capable of switching between the transmission mode state and the blocking mode state is 15 It may be at least%, at least 20%, at least 25%, at least 30%, at least 35% or at least 40%, or at most 90%, at most 85%, at most 80%, at most 75%, at most 70%, at most 65%, 60 Up to 55%, up to 50%, or up to 45%.
  • the above-mentioned transmittance may be, for example, a straight light transmittance.
  • the linear light transmittance is a percentage of the ratio of light transmitted in the same direction as the incidence direction to light incident on the device.
  • the transmittance may be defined as the transmittance. Can be.
  • the reflectance of the optical modulator in the high reflection mode may be at least 10%, at least 15%, at least 20%, at least 25%, at least 30%, at least 35%, or at least 40%.
  • the reflectance of the optical modulation device in the low reflection mode, may be 20% or less, 15% or less, 10% or less, or 5% or less. Since the higher the reflectance is advantageous in the high reflection mode, the lower the reflectance is advantageous in the low reflection mode, so that the upper limit of the reflectance in the high reflection mode state and the lower limit of the reflectance in the low reflection mode state are not particularly limited.
  • the reflectance in the high reflection mode state may be about 60% or less, 55% or less or 50% or less, and the lower limit of the reflectance in the low reflection mode state may be about 0%.
  • the difference between the reflectance in the high reflection mode state and the reflectance in the low reflection mode state (high reflection mode-low) in an optical modulation device capable of switching between the low reflection mode state and the high reflection mode state Reflection mode) may be at least 5%, at least 10% at least 15%, at least 20%, at least 25%, at least 30%, at least 35%, or at least 40%, at most 90%, at most 85%, at most 80%, 75% or less, 70% or less, 65% or less, 60% or less, 55% or less, 50% or less, or 45% or less.
  • the above-mentioned transmittances and reflectances are transmittances or reflectances for any wavelength in the visible light region, for example, in the range of about 400 to 700 nm or about 380 to 780 nm, or transmittances or reflectances for the entire visible light region, or
  • the transmittance or reflectance of the entire visible light region may be the maximum or minimum transmittance or reflectance, or the average value of the transmittance or reflectance in the visible light region.
  • the light modulation device of the present application may be designed to be able to switch between at least two or more states of one state and the other state selected from the above transmission mode, blocking mode, high reflection mode and low reflection mode states. If necessary, other third states including those other than the above state, for example, the state of the intermediate transmittance of the transmission mode and the blocking mode state, the state of the intermediate reflectance of the high reflection mode and the low reflection mode state, and the like, or the like.
  • the above state can also be implemented.
  • the switching of the optical modulation device as described above may be adjusted according to the application of an external signal, for example, the application of a voltage signal.
  • an external signal for example, the application of a voltage signal.
  • the optical modulation device may maintain one of the states described above and then switch to another state when a voltage is applied.
  • By changing the strength, frequency and / or shape of the applied voltage it is also possible to change the state of the mode or to implement the third other mode state.
  • the light modulation device of the present application may basically include a light modulation film layer having two substrates disposed opposite to each other and a light modulation layer positioned between the substrates.
  • a first substrate any one of the two oppositely arranged substrates
  • the other substrate is referred to as a second substrate.
  • FIG. 1 is a cross-sectional view of an exemplary light modulating film layer of the present application, wherein the light modulating film layer is disposed between the first and second substrates 11 and 13 and the first and second polymer film substrates that are disposed to face each other.
  • Light modulating layer 12 present.
  • a polymer film substrate is applied as the substrate.
  • the substrate of the light modulation device may not include a glass layer.
  • a device having no mechanical defects such as rainbow phenomenon and excellent mechanical properties can be formed. This result is contrary to the common knowledge of the prior art that an optically isotropic substrate should be applied to secure excellent optical properties, and that the substrate having isotropic mechanical properties is advantageous in terms of mechanical properties such as dimensional stability of the device.
  • the polymer film substrate that is anisotropic in terms of optical and mechanical properties may be referred to as an asymmetric substrate or an asymmetric polymer film substrate.
  • the optically anisotropic polymer film substrate is a case having the in-plane retardation described above, and the anisotropy in terms of mechanical properties is a case of having the following physical properties.
  • the physical properties of the polymer film substrate referred to in the present specification may be physical properties of the polymer film substrate itself or physical properties in a state in which an electrode layer is formed on one surface of the polymer film substrate.
  • the electrode layer may be an electrode layer formed in a state where the polymer film substrate is included in an optical device.
  • the in-plane retardation of the first and second polymer film substrates may be about 4,000 nm or more, respectively.
  • the in-plane retardation Rin may mean a value calculated by Equation 1 below.
  • Rin d ⁇ (nx-ny)
  • Rin is an in-plane retardation
  • d is a thickness of the polymer film substrate
  • nx is a refractive index in the slow axis direction of the polymer film substrate
  • ny is a refractive index in the fast axis direction, the in-plane direction orthogonal to the slow axis direction Refractive index.
  • the in-plane retardation of the first and second polymer film substrates is 4,000 nm or more, 5,000 nm or more, 6,000 nm or more, 7,000 nm or more, 8,000 nm or more, 9,000 m or more, 10,000 m or more, 11,000 m or more, or 12,000 m or more, respectively. It may be at least 13,000m, at least 14,000m, or at least 15,000m.
  • the in-plane retardation of each of the first and second polymer film substrates may be about 50,000 nm or less, about 40,000 nm or less, about 30,000 nm or less, 20,000 nm or less, 18,000 nm or less, 16,000 nm or less, 15,000 nm or less, or 12,000 nm. It may be less than.
  • the polymer film substrate may be, for example, a polyester film substrate.
  • a representative example of the polymer film substrate is a polyester film such as PET (poly (ethylene terephthalate)) film, for example, a film of the brand name SRF (Super Retardation Film) series supplied by Toyobo have.
  • PET poly (ethylene terephthalate)
  • SRF Super Retardation Film
  • each of the polymer film substrates has a ratio (E1 / E2) of elongation E1 in any first direction in plane and elongation E2 in a second direction perpendicular to the first direction. It may be abnormal.
  • the ratio E1 / E2 may in another example be at least about 3.5, at least 4, at least 4.5, at least 5, at least 5.5, at least 6, or at least 6.5.
  • the ratio E1 / E2 may be about 20 or less, 18 or less, 16 or less, 14 or less, 12 or less, 10 or less, 8 or less, or 7.5 or less.
  • the first, second and third directions of the polymer film substrate are any directions in the plane of the film substrate.
  • the in-plane direction may be an in-plane direction formed by MD (Machine Direction) and TD (transverse direction) directions of the polymer film substrate.
  • the first direction described herein may be one of the slow axis and the fast axis direction of the polymer film substrate
  • the second direction may be the other direction of the slow axis and the fast axis direction.
  • the first direction is any one of a machine direction (MD) and a transverse direction (TD) direction when the polymer film substrate is a stretched polymer film substrate
  • the second direction is a machine direction (MD) and TD ( transverse direction) may be one of the other directions.
  • the first direction of the polymer film substrate referred to herein may be the TD direction or the slow axis direction.
  • the elongation in the first direction (eg, the slow axis direction or the TD direction) of each of the first and second polymer film substrates may be 15% or more or 20% or more.
  • the elongation may in another example be at least about 25%, at least 30%, at least 35% or at least 40%, or at most about 60%, at most 55%, at most 50%, or at most 45%.
  • each of the first and second polymer film substrates may have an elongation (E3) in the third direction forming an angle within the range of 40 degrees to 50 degrees or about 45 degrees, respectively, with the first and second directions. It may be larger than the elongation E1 in one direction, and the ratio E3 / E2 of the elongation E3 in the third direction and the elongation E2 in the second direction may be 5 or more.
  • the ratio E3 / E2 may in another example be at least 5.5, at least 6, at least 6.5, at least 7, at least 7.5, at least 8, or at least 8.5, at most about 20, at most 18, at most 16, at most 14, at most 12, or May be 10 or less.
  • Elongation in the third direction of each of the first and second polymer film substrates may be 30% or more.
  • the elongation may in another example be at least about 35%, at least 40%, at least 45%, at least 50%, or at least 55%, or at most about 80%, at most 75%, at most 70%, or at most 65%.
  • Each of the first and second polymer film substrates may have a ratio (CTE2 / CTE1) of thermal expansion coefficient (CTE2) in the second direction and thermal expansion coefficient (CTE1) in the first direction to be 1.5 or more.
  • the thermal expansion coefficients (CTE1, CTE2) are the values found within the temperature range of 40 ° C to 80 ° C, respectively.
  • the ratio CTE2 / CTE1 may be about 2 or more, about 2.5 or more, 3 or more, or 3.5 or more, or 10 or less, 9 or less, 8 or less, 7 or less, 6 or less, 5 or less, or 4 or less.
  • the coefficient of thermal expansion (CTE2) in the second direction may be in the range of 5 to 150 ppm / ° C.
  • the thermal expansion coefficient is about 10 ppm / ° C or higher, 15 ppm / ° C or higher, 20 ppm / ° C or higher, 25 ppm / ° C or higher, 30 ppm / ° C or higher, 35 ppm / ° C or higher, 40 ppm / ° C or higher, 45 ppm Or at least 50 ° C., at least 50 ppm / ° C., at least about 55 ppm / ° C., at least 60 ppm / ° C., at least 65 ppm / ° C., at least 70 ppm / ° C., at least 75 ppm / ° C., or at least 80 ppm / ° C., or at least 140 ppm / ° C.
  • 130 ppm / ° C or less 120 ppm / ° C or less, 100 ppm / ° C or less, 95 ppm / ° C or less, 90 ppm / ° C or less, 85 ppm / ° C or less, 80 ppm / ° C or less, 40 ppm / ° C or less , 30 ppm / ° C. or less, or 25 ppm / ° C. or less.
  • the first and second polymer film substrates may each have a ratio YM1 / YM2 of 1.5 or more in the second direction and the modulus of elasticity YM2 in the first direction.
  • the ratio YM1 / YM2 may be about 2 or more, 10 or less, 9 or less, 8 or less, 7 or less, 6 or less, 5 or less, 4 or less, 3 or less, or 2.5 or less.
  • the elastic modulus YM1 in the first direction may be in a range of about 2 to 10 GPa.
  • the elastic modulus YM1 is, in another example, about 2.5 GPa or more, 3 GPa or more, 3.5 GPa or more, 4 GPa or more, 4.5 GPa or more, 5 GPa or more or 5.5 GPa or more, about 9.5 GPa or less, 9 GPa or less, 8.5 GPa or less, 8 GPa or less It may be 7.5 GPa or less, 7 GPa or less, 6.5 GPa or less, or 6 GPa or less.
  • the elastic modulus is a so-called Young's modulus and is measured according to the method of the embodiment described later.
  • Each of the first and second polymer film substrates may have a ratio MS1 / MS2 of the maximum stress MS2 in the second direction and the maximum stress MS1 in the first direction, respectively.
  • the ratio MS1 / MS2 may be about 2 or more, 10 or less, 9 or less, 8 or less, 7 or less, 6 or less, 5 or less, 4 or less, 3 or less, or 2.5 or less.
  • the maximum stress MS1 in the first direction may be in a range of about 80 to 300 MPa.
  • the maximum stress MS1 is, in another example, at least about 90 MPa, at least about 100 MPa, at least about 110 MPa, at least about 120 MPa, at least about 130 MPa, at least about 140 MPa, at least about 150 MPa, at least about 155 MPa, 160 MPa or more, 165 MPa or more, 170 MPa or more, 175 MPa or more, or 180 MPa or more, about 300 MPa or less, about 290 MPa or less, about 280 MPa or less, about 270 MPa or less, about 260 MPa or less, about 250 MPa or less, about 245 MPa or less, It may be 240 MPa or less, 235 MPa or less, 230 MPa or less, 225 MPa or less, 220 MPa or less, 215 MPa or less, 210 MPa or less, 205 MPa or less
  • the absolute value of the angle formed between the first direction of the first polymer film substrate and the first direction of the second polymer film substrate is in a range of 0 degrees to 10 degrees or 0 degrees to 5 degrees, Alternatively, the first directions may be substantially horizontal to each other. As described above, the first direction may be a slow axis direction or a TD direction of the polymer film substrate.
  • the optical and mechanical properties can be excellently implemented.
  • a representative example of the polymer film having such a large optical and mechanical asymmetry is a stretched PET (polyethyleneterephtalate) film known as a so-called high-stretch polyester film, and such a film is easily available in the industry.
  • a stretched PET film is one or more layers of uniaxially stretched films produced by melting / extruding PET resins by stretching or stretching, or one or more layers of biaxially stretched films produced by longitudinal and transverse stretching after film formation.
  • PET resin generally means resin in which 80 mol% or more of a repeating unit becomes ethylene terephthalate, and may also contain another dicarboxylic acid component and a diol component.
  • another dicarboxylic acid component For example, isophthalic acid, p-beta-oxyethoxy benzoic acid, 4,4'- dicarboxydiphenyl, 4,4'- dicarboxy benzophenone, bis (4-carboxyphenyl) ethane, adipic acid, sebacic acid and / or 1,4-dicarboxycyclohexane, etc. are mentioned.
  • the other diol component is not particularly limited, but may be propylene glycol, butanediol, neopentyl glycol, diethylene glycol, cyclohexanediol, ethylene oxide adduct of bisphenol A, polyethylene glycol, polypropylene glycol, and / or polytetramethylene glycol. Can be mentioned.
  • the said dicarboxylic acid component and diol component can be used in combination of 2 or more type as needed. Moreover, you may use together oxycarboxylic acids, such as p-oxybenzoic acid. In addition, as the other copolymerization component, a dicarboxylic acid component or a diol component containing a small amount of amide bond, urethane bond, ether bond, carbonate bond, or the like may be used.
  • a method for producing a PET-based resin As a method for producing a PET-based resin, a method of directly polycondensing terephthalic acid, ethylene glycol and / or other dicarboxylic acids or other diols as necessary, dialkyl esters of terephthalic acid and ethylene glycol and / or other dikars as necessary Polycondensation of a dialkyl ester or other diol of an acid followed by a transesterification reaction, and polycondensation of ethylene glycol esters of terephthalic acid and / or other dicarboxylic acids and / or other diol esters as necessary. Method and the like are employed.
  • a polymerization catalyst containing an antimony-based, titanium-based, germanium-based or aluminum-based compound, or a polymerization catalyst containing the complex compound can be used.
  • the polymerization reaction conditions may be appropriately selected depending on the monomers used, the catalyst, the reaction apparatus, and the desired resin physical properties.
  • the reaction temperature is usually about 150 ° C to about 300 ° C and about 200 ° C. To about 300 ° C or about 260 ° C to about 300 ° C.
  • the reaction pressure is usually from atmospheric pressure to about 2.7 Pa, may be on the pressure-reducing side later in the reaction.
  • the polymerization reaction proceeds by volatilizing leaving reactants such as diols, alkyl compounds or water.
  • the polymerization apparatus may be one complete reaction tank, or may be a combination of a plurality of reactors. In this case, depending on the degree of polymerization, the reactants are polymerized while being transferred between the reaction tanks. Moreover, the horizontal reaction apparatus is provided in the latter half of superposition
  • the resin is discharged from the reaction tank or the horizontal reactor in the molten state and then cooled or pulverized in a cooling drum or a cooling belt, or in the form of pellets which have been introduced into an extruder and extruded in a string shape. Obtained.
  • the solid phase polymerization may be carried out to improve the molecular weight or to reduce the low molecular weight component.
  • a low molecular weight component which can be contained in PET resin although a cyclic trimer component is mentioned, content of such a cyclic trimer component in resin is adjusted to 5000 ppm or less or 3000 ppm or less normally.
  • the molecular weight of PET resin is 0.45-1.0 dL / g, 0.50-normally when melt
  • dissolving resin in the mixed solvent of phenol / tetrachloroethane 50/50 (weight ratio), and showing it by the intrinsic viscosity measured at 30 degreeC. 10 dL / g or 0.52 to 0.80 dL / g.
  • PET-based resin can contain an additive as needed.
  • an additive a lubricating agent, an antiblocking agent, a heat stabilizer, antioxidant, an antistatic agent, a light resistant agent, an impact resistance improvement agent, etc. are mentioned, for example. It is preferable to make the addition amount into the range which does not adversely affect optical physical property.
  • PET-based resins are usually used in pellet form assembled by an extruder for blending such additives and for film molding described later.
  • the size and shape of the pellets are not particularly limited, but are usually cylindrical, spherical or flat spherical with a height of 5 mm or less.
  • the PET resin obtained in this manner can be formed into a film shape and stretched to form a PET film having high transparent and homogeneous mechanical strength.
  • the pellet which consists of dried PET resin is supplied to a melt extrusion apparatus, and it heats and melts above melting
  • the molten resin is extruded from the die and quenched and solidified to a temperature below the glass transition temperature on a rotary cooling drum to obtain an unstretched film in a substantially amorphous state.
  • This melting temperature is determined depending on the melting point and the extruder of the PET resin used, and is not particularly limited, but is usually 250 ° C to 350 ° C.
  • the electrostatic application adhesion method usually provides a linear electrode on the upper surface side of the film in a direction orthogonal to the flow of the film, and provides electrostatic charge to the film by applying a DC voltage of about 5 to 10 kV to the electrode, thereby rotating cooling. It is a method of improving the adhesiveness of a drum and a film.
  • the liquid coating adhesion method is a method of improving the adhesiveness of a rotating cooling drum and a film by apply
  • PET resin used can also mix 2 or more types of resin, resin from which a structure and a composition differ as needed. For example, the mixture which uses the pellet which mix
  • the laminated number of the film to extrude can also be made into two or more layers as needed.
  • pellets in which granular fillers as an antiblocking agent are mixed and pellets without blending are prepared, and fed into the same die from different extruders to form a film composed of two or three layers of "filler blending / no blending / filler blending". Extrusion is possible.
  • the unstretched film is usually longitudinally stretched in the extrusion direction at a temperature above the glass transition temperature.
  • the stretching temperature is usually 70 ° C to 150 ° C, 80 to 130 ° C or 90 to 120 ° C.
  • a draw ratio is 1.1 to 6 times or 2 to 5.5 times normally. Stretching may be completed by one time, or may be performed by dividing into multiple times as necessary.
  • the longitudinally stretched film obtained in this way can heat-process after this. Subsequently, a relaxation process may be performed as needed.
  • This heat treatment temperature is 150 degreeC-250 degreeC, 180-245 degreeC, or 200-230 degreeC normally. Further, the heat treatment time is usually 1 to 600 seconds or 1 to 300 seconds or 1 to 60 seconds.
  • the temperature of a relaxation process is 90-200 degreeC or 120-180 degreeC normally.
  • the amount of relaxation is usually 0.1 to 20% or 2 to 5%.
  • the temperature and relaxation amount of this relaxation process can set the relaxation amount and the temperature at the time of a relaxation process so that the thermal contraction rate in 150 degreeC of PET film after a relaxation process may be 2% or less.
  • transverse stretching is normally performed by a tenter after a longitudinal stretch process or after heat processing or a relaxation process as needed.
  • stretching temperature is 70 degreeC-150 degreeC, 80 degreeC-130 degreeC, or 90 degreeC-120 degreeC normally.
  • a draw ratio is 1.1 to 6 times or 2 to 5.5 times normally.
  • the heat treatment temperature is usually 150 ° C to 250 ° C or 180 ° C to 245 ° C or 200 to 230 ° C.
  • the heat treatment time is usually 1 to 600 seconds, 1 to 300 seconds or 1 to 60 seconds.
  • the temperature of a relaxation process is 100-230 degreeC, 110-210 degreeC, or 120-180 degreeC normally.
  • the amount of relaxation is usually 01 to 20%, 1 to 10%, or 2 to 5%.
  • the temperature of this relaxation process and the amount of relaxation can set the amount of relaxation and the temperature at the time of a relaxation process so that the thermal contraction rate in 150 degreeC of PET film after a relaxation process may be 2% or less.
  • stretching direction means the extending
  • the stretching direction refers to a direction perpendicular to the long direction of the film.
  • the stretching is usually performed in the horizontal direction as described above, and in this case, the stretching direction refers to the vertical direction with respect to the longitudinally the same direction.
  • an orientation main axis means the molecular orientation direction in the arbitrary point on a stretched PET film.
  • stretching direction of an orientation main axis means the angle difference of an orientation main axis and an extending direction.
  • the maximum value means the maximum value of the value on a perpendicular direction with respect to a long direction.
  • the confirmation direction of the said orientation main axis is well-known, For example, it measures using retardation film and an optical material inspection apparatus RETS (manufactured by Otsuka Denshi Co., Ltd.) or a molecular orientation system MOA (manufactured by Oji Kiso Co., Ltd.). Can be.
  • RETS optical material inspection apparatus
  • MOA molecular orientation system
  • Anti-glare may be provided to the stretched PET film used by this application.
  • the method of providing anti-glare property is not specifically limited, For example, according to the method of mixing and forming an inorganic fine particle or organic fine particle in the said raw material resin, and the manufacturing method of the said film, an inorganic fine particle or organic fine particle mixes on one side. A coating liquid formed by mixing inorganic fine particles or organic fine particles with a curable binder resin is coated on one side of a stretched film or a stretched PET film with an unstretched layer, and the binder resin is cured to provide an antiglare layer. And the like are employed.
  • the inorganic fine particles for imparting anti-glare properties are not particularly limited, but for example, silica, colloidal silica, alumina, alumina sol, aluminosilicate, alumina-silica composite oxide, kaolin, talc, mica, calcium carbonate and phosphoric acid Calcium etc. are mentioned. Moreover, it is although it does not specifically limit as organic microparticles
  • fine-particles For example, crosslinked polyacrylic acid particle, methyl methacrylate / styrene copolymer resin particle, crosslinked polystyrene particle, crosslinked polymethylmethacrylate particle, silicone resin particle, and polyimide particle Etc. can be mentioned.
  • the haze value of the stretched PET film provided with the anti-glare property obtained in this way may exist in 6 to 45% of range.
  • the said haze value can be measured using the haze transmittance meter HM-150 (manufactured by Matsuki Kiyoshi Co., Ltd.) according to JIS K 7136, for example.
  • the measurement sample which bonded the film surface to the glass substrate so that the anti-glare surface may become a surface using an optically transparent adhesive for example can be used.
  • the method of manufacturing the PET film described above is one exemplary method for obtaining the polymer film substrate of the present application, and any polymerizable product may be used as long as the polymer film substrate applicable in the present application has the above-described physical properties.
  • the polymer film substrate may be a film substrate having an electrode layer formed on one surface thereof.
  • a film substrate may be referred to as an electrode film substrate.
  • the retardation, mechanical properties, and the like described above may be for the polymer film substrate on which the electrode layer is not formed, or for the electrode film substrate.
  • an electrode layer may be formed on at least one surface of the polymer film substrate, and the first and second polymer film substrates may be disposed to face each electrode layer.
  • a known transparent electrode layer may be applied.
  • a so-called conductive polymer layer, a conductive metal layer, a conductive nanowire layer, or a metal oxide layer such as indium tin oxide (ITO) may be used as the electrode layer.
  • ITO indium tin oxide
  • various materials and forming methods capable of forming a transparent electrode layer are known, and this may be applied without limitation.
  • an alignment layer may be formed on one surface of the polymer film substrate.
  • an alignment layer may be formed on the electrode layer.
  • a well-known alignment film can be formed as an alignment film, The kind of alignment film which can be applied according to a desired mode is well-known.
  • the light modulation layer included in the light modulation film layer in the present application is a functional layer that can vary the transmittance, reflectance and / or haze of light depending on whether an external signal is applied.
  • a light modulation layer may be referred to herein as an active light modulation layer.
  • the external signal may mean all factors, for example, an external voltage, etc., which may affect the behavior of a material included in the light modulation layer, for example, the light modulation material. Therefore, the state without an external signal may mean a state without application of an external voltage.
  • the type of light modulation layer in the present application is not particularly limited as long as it has the above-described function, a known light modulation layer can be applied.
  • the light modulation layer may be, for example, a liquid crystal layer, an electrochromic material layer, a photochromic material layer, an electrophoretic material layer, or a dispersed particle alignment layer.
  • the light modulation layer exemplified above will be described with specific examples.
  • the configuration of the light modulation layer is not limited to the following, and the known contents related to the light modulation layer may be applied without limitation to the present application.
  • the liquid crystal layer is a layer containing a liquid crystal compound.
  • the range of the liquid crystal layer includes a mode containing a liquid crystal compound.
  • a so-called guest host layer including a liquid crystal compound (liquid crystal host) and a dichroic dye is also defined herein. It is a kind of liquid crystal layer.
  • the liquid crystal layer may be an active liquid crystal layer, and thus the liquid crystal compound may exist in the liquid crystal layer so that the alignment direction is changed depending on whether an external signal is applied.
  • any kind of liquid crystal compound can be used as long as its orientation can be changed by application of an external signal.
  • liquid crystal compound a smectic liquid crystal compound, a nematic liquid crystal compound, or a cholesteric liquid crystal compound may be used as the liquid crystal compound.
  • the liquid crystal compound may be, for example, a compound having no polymerizable group or a crosslinkable group so that the orientation direction thereof may be changed by application of an external signal.
  • the liquid crystal layer may include a liquid crystal compound having positive or negative dielectric anisotropy.
  • the absolute value of the dielectric anisotropy of the liquid crystal may be appropriately selected in consideration of the purpose of the present application.
  • the term “dielectric anisotropy ( ⁇ )” may mean a difference ( ⁇ // ⁇ ⁇ ) between a horizontal dielectric constant ( ⁇ //) and a vertical dielectric constant ( ⁇ ) of a liquid crystal.
  • the term horizontal permittivity ( ⁇ //) refers to a dielectric constant value measured along the direction of the electric field in a state where a voltage is applied such that the direction of the electric field due to the director and the applied voltage of the liquid crystal molecules is substantially horizontal
  • the vertical dielectric constant ( ⁇ ) refers to a dielectric constant value measured along the direction of the electric field while a voltage is applied such that the direction of the electric field due to the director of the liquid crystal molecules and the applied voltage is substantially perpendicular.
  • the driving mode of the liquid crystal layer may be, for example, a dynamic scattering (DS) mode, an electrically controllable fringefringence (ECB) mode, an in-plane switching (IPS) mode, a fringe-field switching (FFS) mode, or an OCB (optimally compensated bend) mode.
  • DS dynamic scattering
  • EBC electrically controllable fringefringence
  • IPS in-plane switching
  • FFS fringe-field switching
  • OCB optically compensated bend
  • VA vertical alignment
  • MVA multi-domain vertical alignment
  • PVA multi-domain vertical alignment
  • PVA patterned vertical alignment
  • HAN hybrid aligned nematic
  • TN twisted nematic
  • STN super twisted nematic
  • the liquid crystal layer may be a polymer network liquid crystal layer.
  • the polymer network liquid crystal layer is a higher concept including a polymer dispersed liquid crystal layer, a polymer stabilized liquid crystal layer, and the like.
  • the polymer network liquid crystal layer may include, for example, a liquid crystal region including a polymer network and a liquid crystal compound dispersed in a phase separated state from the polymer network.
  • the liquid crystal compound may exist in the polymer network such that the orientation is switchable.
  • the polymer network may be a polymer network of precursors including a polymerizable or crosslinkable compound, and the polymerizable or crosslinkable compound may form a polymer network in a polymerized state or in a crosslinked state.
  • the polymerizable or crosslinkable compound for example, a compound having a meta) acryloyl group may be used, but is not limited thereto.
  • the liquid crystal layer may be a pixel isolated liquid crystal layer (PILC).
  • PILC pixel isolated liquid crystal layer
  • the pixel-isolated liquid crystal layer refers to a liquid crystal layer in which a partition structure for maintaining a gap of a cell is introduced for each pixel.
  • the pixel-isolated liquid crystal layer may include a liquid crystal compound whose alignment direction may be changed by a signal applied from the outside.
  • the pixel isolated liquid crystal layer can also adjust the light transmittance by using the alignment state of such a liquid crystal compound.
  • the electrochromic material layer uses a phenomenon in which the light transmittance of the electrochromic material is changed by, for example, an electrochemical redox reaction.
  • the electrochromic material may be colored in the state in which the electrical signal is applied, and may be colored in the state in which the electrical signal is applied, thereby adjusting the light transmittance.
  • the photochromic material layer may vary the light transmittance using, for example, a phenomenon in which the binding state of the photochromic material is changed to change color (reversibly) when light of a specific wavelength is irradiated.
  • the photochromic material is colored when exposed to ultraviolet rays and becomes inherently pale when irradiated with visible light, but is not limited thereto.
  • the layer of electrophoretic material may vary the light transmittance, for example, by the combination of the medium liquid and the electrophoretic material.
  • the electrophoretic material particles having a positive (+) or negative (-) charge and having a color may be used, and are applied to two electrodes located above and below the layer of the electrophoretic material. Electrophoretic particles may be rotated according to the voltage, or the light transmittance may be adjusted in a manner of moving closer to the electrode having different polarities, but the present invention is not limited thereto.
  • the dispersed particle alignment layer includes, for example, a structure in which a thin film laminate of nano-sized rod-shaped particles is suspended in a liquid crystal.
  • the dispersed particle alignment layer may, for example, exist in a state in which floating particles are not aligned in the state in which no external signal is applied, thereby blocking and absorbing light, and aligning the floating particles in the state in which the external signal is applied to pass the light.
  • the present invention is not limited thereto.
  • the light modulating layer may further include a dichroic dye in terms of adjusting light transmittance variable characteristics.
  • a dichroic dye in terms of adjusting light transmittance variable characteristics.
  • the term “dye” may mean a material capable of intensively absorbing and / or modifying light in at least part or the entire range within the visible light region, for example, in the 400 nm to 700 nm wavelength range
  • the term “dichroic dye” may refer to a material capable of anisotropic absorption of light in at least part or entire range of the visible light region. Such dyes are known, for example, but not limited to azo dyes, anthraquinone dyes, and the like.
  • the light modulation layer is a liquid crystal layer including a liquid crystal and a dichroic dye, and may be a so-called guest host liquid crystal cell.
  • the term "GHLC layer” may mean a functional layer in which dichroic dyes are arranged together according to the arrangement of liquid crystals, and exhibit anisotropic light absorption characteristics with respect to the alignment direction of the dichroic dye and the vertical direction of the alignment direction, respectively. have.
  • a dichroic dye is a material whose light absorption varies depending on the polarization direction. When the absorption rate of light polarized in the long axis direction is large, it is called a p-type dye.
  • the absorption rate of light polarized in the short axis direction is large, it is called an n-type dye. It can be called.
  • the polarized light vibrating in the long axis direction of the dye is absorbed and the polarized light vibrating in the short axis direction of the dye is less absorbed and thus can be transmitted.
  • the dichroic dye is assumed to be a p-type dye.
  • the optical modulation film layer including the guest host liquid crystal layer as an optical modulation layer may function as an active polarizer.
  • active polarizer may refer to a functional device capable of adjusting anisotropic light absorption according to application of an external signal. Such an active polarizer may be distinguished from a passive polarizer, which will be described later, having a constant light absorption or light reflection characteristic regardless of external signal application.
  • the guest host liquid crystal layer may control anisotropic light absorption for polarization in a direction parallel to the arrangement direction of the dichroic dye and polarization in a vertical direction by adjusting the arrangement of the liquid crystal and the dichroic dye. Since the arrangement of the liquid crystal and the dichroic dye may be controlled by application of an external signal such as a magnetic field or an electric field, the guest host liquid crystal layer may control anisotropic light absorption according to the application of the external signal.
  • the thickness of the light modulation layer may be appropriately selected in consideration of the purpose of the present application, respectively.
  • the thickness of the optical modulation layer is about 0.01 ⁇ m or more, 0.1 ⁇ m or more, 1 ⁇ m or more, 2 ⁇ m or more, 3 ⁇ m or more, 4 ⁇ m or more, 5 ⁇ m or more, 6 ⁇ m or more, 7 ⁇ m or more, and 8 ⁇ m. Or more, 9 ⁇ m or more or 10 ⁇ m or more.
  • the thickness is not particularly limited as the thickness can be realized a difference in transmittance and / or reflectance, but may generally be about 30 ⁇ m or less, 25 ⁇ m or less, 20 ⁇ m or less or 15 ⁇ m or less.
  • the optical modulation layer is a liquid crystal layer
  • an optical axis in a specific state of the optical modulation layer and a first direction of the polymer film substrate (for example, the slow axis direction or the TD direction described above)
  • the optical properties can be further improved.
  • a method of implementing the above-described type of light modulating film layer may be a known method except for disposing the polymer film substrate as the substrate in the above-described manner.
  • the light modulating film layer may include a spacer, a sealant, or the like, which maintains a space between the substrates in addition to a known structure, for example, the substrate, the light modulation layer, and the electrode layer.
  • the light modulation device of the present application basically includes the above-mentioned light modulating film layer, but may include additional other configurations as necessary. That is, depending on the driving mode, the light modulation film layer alone may implement the above-described transmission, blocking, high reflection, and / or low reflection modes, and switching therebetween, but in order to facilitate implementation or switching of these modes. Inclusion of additional configurations is also possible.
  • the device may further include a polarizer (passive polarizer) disposed on at least one side of the light modulating film layer.
  • a polarizer passive polarizer
  • 2 illustrates an example in which the polarizer 14 is disposed on one side of the light modulation film layer having the light modulation layer 12 positioned between the first and second polymer film substrates 11 and 13. Shows.
  • the angle between the transmission axis, absorption axis or reflection axis of the passive polarizer and the first direction (eg, the slow axis direction or the TD direction) of the polymer film substrate is 0 degrees to 10 degrees, 0 degrees. It may be from 5 degrees or approximately 0 degrees, or in the range of 80 degrees to 100 degrees, in the range of 85 degrees to 95 degrees or approximately 90 degrees.
  • the angle is an acute angle among angles formed by the transmission axis, the absorption axis or the reflection axis, and the first direction (for example, the slow axis direction or the TD direction described above). This arrangement can further improve optical and mechanical properties.
  • the optical axis during the horizontal alignment of the light modulation layer may be in a first direction of the first and second polymer film substrates.
  • the slow axis direction or the TD direction and an angle of 0 degrees to 10 degrees, 0 degrees to 5 degrees, or approximately 0 degrees, or 80 degrees to 100 degrees, 85 degrees to 95 degrees, or approximately 90 degrees. .
  • the term polarizer may refer to a device for converting natural light to non-polarized light into polarized light.
  • the definitions of the passive polarizer and the active polarizer are as described above.
  • the polarizer may be a linear polarizer.
  • the linearly polarized light refers to a case in which the light selectively transmitting is linearly polarized by vibrating in one direction, and the light selectively absorbing or reflecting is linearly polarized by vibrating in a direction perpendicular to the vibration direction of the linearly polarized light. That is, the linear polarizer may have a transmission axis and an absorption axis or a reflection axis that are perpendicular to each other in the plane direction.
  • the polarizer may be an absorbing polarizer or a reflective polarizer.
  • the absorption polarizer for example, a polarizer in which iodine is impregnated in a polymer stretched film such as a poly (vinyl alcohol) stretched film or the like, or a liquid crystal polymerized in an oriented state is used as a host.
  • a guest-host polarizer with a dichroic dye arranged as a guest may be used, but is not limited thereto.
  • a reflective polarizer for example, a reflective polarizer known as a dual brightness enhancement film (DBEF) or a reflective polarizer formed by coating a liquid crystal compound such as LLC (Lyotropic liquid crystal) may be used. It is not limited to this.
  • DBEF dual brightness enhancement film
  • LLC Low-density liquid crystal
  • the light modulation device may have a structure in which the polarizers are disposed on both sides of the light modulation film layer.
  • the angle formed by the transmission axis of the polarizers disposed on both sides may be in a range of about 85 degrees to about 95 degrees or approximately perpendicular.
  • the light modulation device of the present application may include two or more light modulation film layers.
  • each of the light modulation film layers may include two substrates, or at least one substrate may be shared.
  • the optical modulation device may have a structure of a first substrate, a first light modulation layer, a second substrate, a third substrate, a second light modulation layer, and a fourth substrate sequentially stacked, or the first stacked sequentially. It may have a structure of a substrate, a first light modulation layer, a second substrate, a second light modulation layer and a third substrate.
  • at least two substrates in the structure may be the above-mentioned asymmetric polymer film substrate, or all the substrates may be the asymmetric polymer film substrate.
  • the angle formed by the first directions (for example, the above-described slow axis direction or the TD direction) of all the polymer film substrates is 0 to 10 degrees. It may be in the range of degrees to 5 degrees or approximately 0 degrees.
  • the optical modulation device is a first optical modulation positioned between the first to third polymer film substrates 21, 23 and 25, and the first and second polymer film substrates 21 and 23, which are sequentially overlapped with each other.
  • a second light modulation layer 24 positioned between the second and third polymer film substrates 23 and 25.
  • the two or more polymer film substrates overlap each other and may mean that light transmitted through one polymer film substrate may be incident on another polymer film substrate.
  • At least two or more of the first to third polymer film substrates may be the above-described asymmetric polymer film substrate, all may be the asymmetric polymer film substrate.
  • the first direction (for example, the above-described slow axis direction or the TD direction) of each of the first and third polymer film substrates is 0 degrees to 10 degrees or 0 degrees to each other. It may be at an angle within the range of 5 degrees, or approximately horizontal to each other.
  • the angle formed by the slow axis direction or the TD direction) may be in a range of 0 degrees to 10 degrees, 0 degrees to 5 degrees, or about 0 degrees, within a range of 80 degrees to 100 degrees, 85 degrees to 95 degrees, or about 90 degrees.
  • the optical modulation device may include: first to fourth polymer film substrates 31, 33, 34 and 36 sequentially arranged to overlap each other; A first light modulation layer (32) positioned between the first and second polymer film substrates (31, 33); And a second light modulation layer 35 positioned between the third and fourth polymer film substrates 34 and 36.
  • At least two or more, for example, all of the first to fourth polymer film substrates may be the above-mentioned asymmetric polymer film substrates.
  • the first direction (eg, the slow axis direction or the TD direction) of the second and third polymer film substrates is disposed to be approximately 0 degrees to 10 degrees, 0 degrees to 5 degrees, or 0 degrees to each other. Can be.
  • the first direction of the first and fourth polymer film substrates (eg, the slow axis direction or the TD direction described above) and the first direction of the second and third polymer film substrates (eg, The above-described slow axis direction or TD direction) may be approximately 0 degrees to 10 degrees, 0 degrees to 5 degrees or approximately 0 degrees, or may be in the range of approximately 80 degrees to 100 degrees, 85 degrees to 95 degrees, or approximately 90 degrees. have.
  • an optical modulation device comprising the two or more light modulation film layers
  • the first and second light modulation layer may be a liquid crystal layer which may exist in a horizontal alignment state, respectively, and the horizontal alignment of the first and second light modulation layers
  • the optical axis of the time is in the range of 0 degrees to 10 degrees, in the range of 0 degrees to 5 degrees or in the range of approximately 0 degrees, in the range of 80 degrees to 100 degrees, in the range of 0 degrees to 10 degrees with the first direction of the first to fourth polymer film substrates It may be in the range of degrees to 95 degrees, or at an angle of approximately 90 degrees.
  • the term horizontal alignment state refers to a state in which the directors of the liquid crystal compound of the light modulation layer are arranged substantially parallel to the plane of the liquid crystal layer, for example, 0 degrees to 10 degrees, 0 degrees to 5 degrees, or about 0 degrees. It can mean the arrangement state.
  • the term vertical alignment state refers to a state in which the directors of the liquid crystal compound of the light modulation layer are arranged approximately perpendicular to the plane of the liquid crystal layer, for example, about 80 to 100 degrees or 85 to 95 degrees or about 90 degrees. It may mean an array state forming a.
  • the director of the liquid crystal molecules or the liquid crystal compound may mean an optical axis or a slow axis of the liquid crystal layer.
  • the direction of the liquid crystal molecules may mean a long axis direction when the liquid crystal molecules are rod-shaped, and may mean an axis in the normal direction of the disc plane when the liquid crystal molecules are discotic.
  • the optical modulation device of the present application includes the first and second optical modulation layers
  • the optical modulation device has an excellent left and right by reducing the difference in contrast ratio in the left and right viewing angles by adjusting the optical axis in the horizontal alignment between the first and second light modulation layers. Symmetry can be secured.
  • the first and second light modulation layers may be liquid crystal layers capable of switching between vertical alignment and horizontal alignment states, respectively, wherein the optical axes of the first and second light modulation layers may be It may be in the range of about 80 degrees to 100 degrees, in the range of about 85 degrees to 95 degrees, or about 90 degrees.
  • the first optical modulation layer 10 is such that the optical axis OA in the horizontal alignment forms an angle within a range of 40 degrees to 50 degrees clockwise with respect to the horizontal axis WA.
  • the optical axis OA in the horizontal alignment of the second optical modulation layer 20 may form an angle within a range of 130 degrees to 140 degrees in the clockwise direction with respect to the optical modulation layer horizontal axis WA.
  • the optical axis of the optical modulation layer as described above is usually determined according to the alignment direction of the alignment film, and the optical modulation layer can be measured in the following manner.
  • an absorption type linear polarizer may be disposed on one surface of the light modulation layer in a state where the first or second light modulation layer is horizontally aligned, and the transmittance may be measured by rotating the polarizer 360 degrees. That is, the optical axis direction can be confirmed by measuring luminance (transmittance) at the other side while irradiating light to the light modulation layer or the absorption type linear polarizer side in the above state. For example, when the transmittance becomes minimum in the process of rotating the polarizer 360 degrees, an angle perpendicular to the absorption axis of the polarizer or a horizontal angle may be defined as the direction of the optical axis.
  • the horizontal axis WA of the optical modulation layer is a direction parallel to the long axis direction of the optical modulation layer or the amount of the observer wearing the eyewear or the observer who observes the display device when applied to the eyewear or the display device. It can mean the direction parallel to the line connecting the eyes.
  • the alignment layer described above may be formed on both sides of the optical modulation layer.
  • the alignment layer may be a vertical alignment layer.
  • the light modulation device may include a first polymer film substrate, a first alignment layer, a light modulation layer, a second alignment layer, a second polymer film substrate and a polarizer in sequence.
  • the optical modulation device may include a first polymer film substrate, a first vertical alignment layer, a first light modulation layer, a second vertical alignment layer, a second polymer film substrate, a third vertical alignment layer, and a second The light modulation layer, the fourth vertical alignment layer and the third polymer film substrate may be sequentially included.
  • the optical modulation device includes a first polymer film substrate, a first vertical alignment layer, a first light modulation layer, a second vertical alignment layer, a second polymer film substrate, a third polymer film substrate, The third vertical alignment layer, the second light modulation layer, the fourth vertical alignment layer and the fourth polymer film substrate may be included.
  • the light modulation device of the present application can adjust the transmittance, reflectivity, and haze by adjusting the orientation direction of the light modulation layer when voltage is not applied and / or when voltage is applied.
  • the orientation direction may be adjusted by adjusting the pretilt angle and the pretilt direction of the alignment layer.
  • the pretilt may have an angle and a direction.
  • the pretilt angle may be referred to as a polar angle, and the pretilt direction may be referred to as an azimuthal angle.
  • the pretilt angle may mean an angle formed by the director of the liquid crystal molecules with respect to a plane parallel to the alignment layer or an angle formed by the surface normal direction of the light modulation layer.
  • the pretilt angle of the vertical alignment layer may induce a vertical alignment state when no voltage is applied to the liquid crystal cell.
  • the first to fourth vertical alignment layer may have a pretilt angle within a range of 70 degrees to 89 degrees.
  • the pretilt angle may be about 71 degrees or more, 72 degrees or more, about 73 degrees or more, or about 74 degrees or more, and about 88.5 degrees or less or about 88 degrees or less in one example.
  • the pretilt angle of the first vertical alignment layer is an angle measured in a clockwise or counterclockwise direction with respect to the plane parallel to the alignment layer, and the pretilt angle of the second vertical alignment layer is opposite to that of the first vertical alignment layer.
  • the pretilt angle of the first vertical alignment layer is measured in the clockwise direction
  • the counterclockwise direction or the pretilt angle of the first vertical alignment layer may be measured in the clockwise direction.
  • the pretilt angle of the third vertical alignment layer is an angle measured in a clockwise or counterclockwise direction with respect to the plane parallel to the alignment layer, and the pretilt angle of the fourth vertical alignment layer is opposite to that of the third vertical alignment layer.
  • the pretilt angle of the vertical alignment layer is measured in the clockwise direction
  • the counterclockwise direction or the pretilt angle of the third vertical alignment layer may be measured in the clockwise direction.
  • the pretilt direction may refer to a direction in which the director of the liquid crystal molecules is projected onto the horizontal surface of the alignment layer.
  • the pretilt direction may be an angle formed between the projected direction and the horizontal axis WA.
  • the pretilt direction of the vertical alignment layer may induce an alignment direction of a horizontal alignment state when voltage is applied to the liquid crystal cell.
  • the pretilt direction of the first and second vertical alignment layers and the pretilt direction of the third and fourth vertical alignment layers may cross each other.
  • the pretilt direction of the first and second vertical alignment layers and the pretilt direction of the third and fourth vertical alignment layers may be perpendicular to each other, for example, 85 degrees to 95 degrees, or about 90 degrees. .
  • the pretilt direction satisfies the above condition, it is possible to provide an optical modulation device having excellent light blocking rate when voltage is applied.
  • any one of the pretilt direction of the first and second vertical alignment layers and the pretilt direction of the third and fourth vertical alignment layers has an optical axis OA within a range of 40 degrees to 50 degrees in the clockwise direction with respect to the horizontal axis WA of the optical modulation layer, and in another direction, for example, the third and fourth vertical alignment layers.
  • the pretilt direction may have an optical axis OA within a range of 130 degrees to 140 degrees in the clockwise direction with respect to the horizontal axis WA of the optical modulation layer.
  • the above-mentioned pretilt angle and direction may be the pretilt angle and direction measured in each liquid crystal layer when the liquid crystal layer is in a vertical alignment state in one example.
  • the first to fourth vertical alignment layers may be a rubbing alignment layer or a photo alignment layer.
  • an orientation direction is determined by a rubbing direction
  • a photo alignment film it is determined by the polarization direction etc. of the light irradiated.
  • the pretilt angle and the pretilt direction of the vertical alignment layer are based on an alignment condition, for example, rubbing conditions and pressure conditions during rubbing orientation, or a light alignment condition, for example, a polarization state of light, an irradiation angle of light, an irradiation intensity of light, and the like. It can be implemented with appropriate adjustments.
  • the pretilt angle may be achieved by controlling the rubbing intensity of the rubbing alignment layer, etc.
  • the pretilt direction may be achieved by controlling the rubbing direction of the rubbing alignment layer.
  • Such an attainment method is a known method.
  • the photo-alignment film it can be achieved by the alignment film material, the direction of polarization applied to the alignment, the state or intensity, and the like.
  • the first to fourth vertical alignment layer may be a rubbing alignment layer.
  • Each of the first to fourth vertical alignment layers may have a unique orientation direction.
  • the rubbing directions of the first and second vertical alignment layers may be about 170 degrees to 190 degrees as opposite directions, and the rubbing directions of the third and fourth vertical alignment layers may be about 170 degrees to the opposite direction. 190 degrees can be achieved.
  • the rubbing direction can be confirmed by measuring the pretilt angle.
  • the rubbing direction is measured by measuring the pretilt angle in the manner described in the following examples. Measurement may be possible.
  • the direction RA of the rubbing orientation of the first vertical alignment layer 12 is 40 degrees to 50 degrees
  • the direction of rubbing orientation of the second vertical alignment layer 14 ( RA) is 220 degrees to 230 degrees
  • the direction RA of the rubbing orientation of the third vertical alignment layer 22 is 130 degrees to 140 degrees
  • the direction RA of the rubbing orientation of the fourth vertical alignment layer 24 May be 310 degrees to 320 degrees.
  • the direction RA of each rubbing orientation is an angle measured in a clockwise or counterclockwise direction with respect to the horizontal axis WA.
  • the direction for measuring the direction RA of each rubbing orientation is selected by measuring only one of the clockwise or counterclockwise directions.
  • the exemplary light modulation device may further include the above-described electrode layer disposed outside the first to fourth alignment layers.
  • the outer side of the configuration may mean the side opposite to the side where the light modulation layer is present.
  • the electrode films disposed on the outside of the first to fourth alignment layers may be referred to as first to fourth electrode layers, respectively.
  • the electrode layer may include a transparent electrode layer.
  • the electrode layer may take over an electric field suitable for the light modulation layer so as to switch the alignment state of the light modulation layer.
  • the direction of the electric field may be a vertical or horizontal direction, for example, a thickness direction or a surface direction of the light modulation layer.
  • the light modulation device of the present application may further include an adhesive.
  • the light modulating film layer and the polarizer may be present in a state of being bonded to each other by the pressure-sensitive adhesive.
  • the first and second light modulation film layers may be present in a state in which they are bonded to each other by the adhesive.
  • the adhesive layer used for adhesion of an optical member can be selected suitably, and can be used.
  • the thickness of the pressure-sensitive adhesive may be appropriately selected in consideration of the purpose of the present application.
  • the light modulation device of the present application may further include a hard coating film.
  • the hard coat film may include a base film and a hard coat layer on the base film.
  • the hard coat film may be used by appropriately selecting a known hard coat film in consideration of the purpose of the present application.
  • the thickness of the hard coat film may be appropriately selected in consideration of the purpose of the present application.
  • the hard coating film may be formed through an adhesive on the outside of the light modulation device.
  • the light modulation device of the present application may further include an antireflection film.
  • the anti-reflection film may include a base film and an anti-reflection layer on the base film.
  • the antireflection film can be appropriately selected from a known antireflection film.
  • the thickness of the antireflection film may be appropriately selected in consideration of the purpose of the present application.
  • the light modulation device of the present application may further include a layer of dye having a near-infrared (NIR) cut function.
  • the dye may be added to block the IR of the region corresponding to the dominant wavelength of the IR sensor to exclude sensor malfunction due to external light components.
  • the dye may be coated on one surface of the first to fourth polymer film substrates or may be used by adding to the pressure-sensitive adhesive or adhesive when the first and second light modulation film layers are bonded to the pressure-sensitive adhesive or adhesive.
  • the anti-reflection film may be formed through an adhesive on the outside of the light modulation device.
  • Such an optical modulation device can be applied to various applications.
  • applications to which the optical modulation device may be applied include openings and eyewear in enclosed spaces including buildings, containers, vehicles, etc., such as windows or sunroofs.
  • the eyewear may include all eyewear configured to allow the observer to observe the outside through a lens, such as general glasses, sunglasses, sports goggles or a helmet, or an augmented reality experience device.
  • An eyewear is a representative application to which the light modulation device of the present application can be applied.
  • sunglasses, sports goggles and augmented reality experience devices such as eyewear in which the lens is mounted so as to be inclined with the observer's frontal view is commercially available.
  • the optical modulation device of the present application can be effectively applied to the eyewear described above.
  • the structure of the eyewear is not particularly limited. That is, the light modulation device may be mounted and applied in the left eye and / or right eye lens of a known eyewear structure.
  • the eyewear includes a left eye lens and a right eye lens; And a frame supporting the left eye lens and the right eye lens.
  • FIG. 7 is an exemplary schematic diagram of the eyewear, a schematic diagram of the eyewear including the frame 82 and the left and right eye lenses 84, but the structure of the eyewear to which the optical modulation device of the present application can be applied. Is not limited to FIG. 9.
  • the left eye lens and the right eye lens may each include the light modulation device.
  • Such a lens may include only the light modulation device or other configuration.
  • the eyewear is not particularly limited in other configurations or designs, and a known method may be applied.
  • 1 to 4 are schematic diagrams of exemplary light modulation devices of the present application.
  • FIG 5 shows an optical axis in the horizontal alignment state of the first and second light modulation layers.
  • FIG. 6 illustrates a pretilt direction of the first to fourth vertical alignment layers.
  • the polymer film substrates applied in Examples or Comparative Examples include a PC (Polycarbonate) film substrate (PC substrate, thickness: 100 ⁇ m, manufacturer: Teijin, product name: PFC100-D150), which is an isotropic film substrate commonly applied as a substrate, and the present application.
  • PC Polycarbonate
  • PET Polyethylene terephthalate
  • SRF substrate thickness: 80 ⁇ m, manufacturer: Toyobo, product name: TA044
  • ITO Indium Tin
  • the in-plane retardation value (Rin) of the polymer film substrate was measured for light having a wavelength of 550 nm using Agilent's UV / VIS spectroscope 8453 device according to the following method. Two polarizers are installed on the UV / VIS spectroscope so that the transmission axes are perpendicular to each other, and the slow axis of the polymer film is disposed between the two polarizers so as to form 45 degrees with the transmission axes of the two polarizers, respectively. was measured. The phase retardation order of each peak is calculated from the transmittance graph according to the wavelength.
  • Equation A the waveform in the transmittance graph according to the wavelength satisfies Equation A below, and the maximum peak Tmax condition in the sine waveform satisfies Equation B below.
  • ⁇ max in the expression A since the T of the expression A and the T of the expression B are the same, the expression is expanded.
  • Formulas are also developed for n + 1, n + 2 and n + 3, n and n + 1 formulas are summarized, R is eliminated, and n is arranged into ⁇ n and ⁇ n + 1 formulas. Since n and ⁇ can be known based on the same T in Equation A and T in Equation B, R is obtained for each of ⁇ n, ⁇ n + 1, ⁇ n + 2 and ⁇ n + 3.
  • the Y value when 550 nm is substituted into the function x is the Rin value for light of 550 nm wavelength.
  • n ( ⁇ n -3 ⁇ n + 1) / (2 ⁇ n + 1 + 1-2 ⁇ n)
  • R in-plane retardation (Rin)
  • means wavelength
  • n vertex order of sinusoidal waveform
  • the Young's modulus, elongation and maximum stress of the polymer film substrates were tensile at 10 mm / min at room temperature (25 ° C) using a universal testing machine (UTM) instrument (Instron 3342). The force was applied at a speed and measured by a tensile strength test according to the specification. In this case, each specimen was prepared by cutting so that the width was about 10 mm and the length was about 30 mm, and each 10 mm of each end of the longitudinal direction was taped to fix the equipment and then evaluated.
  • the coefficient of thermal expansion was measured in accordance with the specification using a TMA (Thermomechanical Analysis) equipment (Metteler toledo, SDTA840), proceeding the length expansion test while increasing the temperature from 40 °C to 80 °C at a rate of 10 °C / min.
  • the measurement direction length of the specimen was 10 mm at the time of measurement, and the load was set to 0.02N.
  • MD and TD are MD (Machine Direction) and TD (transverse direction) directions of a PC substrate and an SRF substrate, respectively, which are stretched films, and 45 is a direction forming 45 degrees with both the MD and TD directions.
  • Two SRF substrates were used to fabricate the light modulation device.
  • An alignment layer was formed on an indium tin oxide (ITO) film (electrode layer) of the SRF substrate (width: 15 cm, length: 5 cm) to prepare a first substrate.
  • ITO indium tin oxide
  • the alignment film one obtained by rubbing treatment of a polyimide-based horizontal alignment film (SE-7492, Nissan) having a thickness of 300 nm with a rubbing cloth was used.
  • SE-7492, Nissan polyimide-based horizontal alignment film having a thickness of 300 nm with a rubbing cloth was used.
  • a second substrate was prepared in the same manner as the first substrate.
  • a GHLC mixture comprising a liquid crystal compound and a dichroic dye having a dielectric constant anisotropy having a refractive index anisotropy ( ⁇ n) of 0.13 therebetween, with the first and second substrates facing each other so as to face each other.
  • MDA- GHLC mixture
  • a composition containing a chiral dopant S811, Merck
  • the TD directions (ground axis directions) of the first and second substrates are respectively 0 degrees with respect to the rubbing axis of the first substrate alignment layer, and the rubbing directions of the first and second alignment layers are 90 degrees to each other.
  • the obtained optical modulation layer was STN mode liquid crystal layer whose twist angle was about 270 degree
  • the linear light transmittance of the light modulating film layer when no voltage is applied is about 28.0%, and when the voltage of about 15V is applied, the linear light transmittance is about 62.7%, and the device can switch between transmission and blocking modes.
  • permeability is a transmittance
  • An optical modulation device was manufactured in the same manner as in Example 1 except that a PC substrate was applied as the substrate.
  • Example 1 Using the optical modulation device of Example 1 and Comparative Example 1 was prepared an eyewear device of the type shown in Figures 8 and 9, the thermal shock test was carried out while the device is bent. Thermal shock test is to raise the eyewear at a temperature increase rate of about 16.25 ° C / min from about -40 ° C to 90 ° C for 10 minutes, then again at a temperature reduction rate of about 16.25 ° C / min. After the temperature was lowered to a temperature and maintained for 10 minutes, the cycle was performed under the condition of repeating the cycle 500 times, and the test was performed while the eyewear was attached to a bending jig having a radius of curvature of about 100 R. It was. 8 is a case of Example 1, Figure 9 is a case of Comparative Example 1, a severe crack was observed in the case of Comparative Example 1 as shown.
  • a light modulating film layer was manufactured in the same manner as in Example 1, but the first direction (TD direction) of the first and second substrates was 90 degrees to each other. At this time, the first direction of the first substrate was 0 degrees and the first direction of the second substrate was 90 degrees based on the rubbing direction of the alignment film on the first substrate.
  • a light modulating film layer was manufactured in the same manner as in Example 1, but the first direction (TD direction) of the first and second substrates was 90 degrees to each other. At this time, the first direction of the first substrate was 45 degrees and the first direction of the second substrate was 135 degrees based on the rubbing direction of the alignment film on the first substrate.
  • the void generation was evaluated while the devices of Example 1, Comparative Examples 2 and 3 were stored at 60 ° C. temperature and 85% relative humidity, respectively, and the results are shown in Table 2 below. Specifically, it was evaluated whether or not voids visually recognized in the light modulation layer while being stored in the above conditions. In general, the size of the visible void is about 10 ⁇ m.
  • Example 1 no void was observed within 500 hours, and the time when the void was first observed was about 504 hours.
  • the light modulation device of the structure of FIG. 4 was manufactured.
  • the SRF substrate was used as the first to fourth polymer film substrates 31, 33, 34, 36.
  • a vertical alignment layer (PVM-11 polyimide layer of Hanchem Co., Ltd.) was formed on the ITO layer of the SRF substrate, and as a light modulation layer, a guest host liquid crystal layer including a liquid crystal and a dichroic dye was prepared.
  • HNG730200 (ne: 1.551, no: 1.476, ⁇ ⁇ : 9.6, ⁇ ⁇ : 9.6, TNI: 100, ⁇ n: 0.075, ⁇ : -5.7) were prepared, and BA12 X12 was prepared as the dichroic dye. did.
  • the vertical alignment layer was coated by bar coating on the ITO layer of the polymer film substrate, and then baked at 120 ° C. for 1 hour to obtain an alignment layer having a thickness of 300 nm.
  • the alignment film was rubbed with a rubbing cloth to prepare a first polymer film substrate.
  • column spacers having a height of 10 ⁇ m and a diameter of 15 ⁇ m are arranged at intervals of 250 ⁇ m on the same ITO layer of the polymer film substrate as described above, and a rubbing treatment is performed by coating a vertical alignment layer with a bar coating on the ITO film.
  • a polymer film substrate was prepared.
  • the third substrate 34, the fourth substrate 36, and the second light modulation layer 35 of FIG. 4 were formed to manufacture a second light modulation film layer.
  • the light modulation device of Example 2 was manufactured by attaching the first light modulation film layer and the second light modulation film layer so that the rubbing directions of the alignment films of each other were perpendicular to each other by 90 degrees.
  • the thicknesses (cell gaps) of the first and second light modulation layers 32 and 35 are 12 ⁇ m, respectively.
  • the first direction (TD direction, slow axis direction) of the first substrate is 0 degrees
  • the first direction (TD direction, slow axis direction) of the second to fourth substrates is also 0.
  • the optical axis in the horizontal alignment of the first optical modulation layer is 0 degrees
  • the optical axis in the horizontal alignment of the second optical modulation layer is 90 degrees.
  • Example 2 when the 1st direction (TD direction, slow-axis direction) of a 1st board
  • Example 2 except that the optical axis in the horizontal alignment of the first optical modulation layer was changed to +45 degrees, and the optical axis in the horizontal alignment of the second optical modulation layer was changed to ⁇ 45 degrees.
  • the light modulation device was manufactured in the same manner.
  • the electro-optical characteristic is that the electrode layers of the first and third polymer film substrates are connected to one terminal among the electrode layers of the first to fourth polymer film substrates of the optical modulation device, and the electrode layers of the second and third polymer film substrates are connected to one terminal.
  • the contrast ratio CR is the ratio (Tc / T) of the transmittance T at the time of application of the 28V voltage to the transmittance Tc in the voltage-free state.
  • Example 1 Example 2 Example 3 Rainbow radish radish radish Transmittance (0V) 44.4% 44.3% 45.6% Transmittance (28V) 2.42% 2.17% 12.44% CR 19.3: 1 20.4: 1 3.7: 1 dC * 13.8 14.3 8.3

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Abstract

La présente invention concerne un dispositif de modulation optique et son utilisation, et peut fournir un dispositif de modulation optique ayant d'excellentes propriétés optiques et mécaniques par application, en tant que substrat, d'un film polymère ayant à la fois une anisotropie optique et une anisotropie mécanique. En outre, la présente invention peut fournir des lunettes comprenant un dispositif de modulation optique qui comprend un substrat de film polymère souple et peut être appliqué à diverses conceptions, telles qu'une forme de pliage.
PCT/KR2018/005021 2017-04-28 2018-04-30 Dispositif de modulation optique WO2018199720A1 (fr)

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US16/500,248 US11347080B2 (en) 2017-04-28 2018-04-30 Light modulation device
CN201880027094.8A CN110546553B (zh) 2017-04-28 2018-04-30 光调制装置
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PCT/KR2018/005017 WO2018199717A1 (fr) 2017-04-28 2018-04-30 Dispositif de modulation de lumière
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TWI771661B (zh) * 2020-03-06 2022-07-21 摩爾應材有限公司 可撓性薄膜、眼睛鏡片、眼睛鏡片收納器、及其操作方法
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CN112432904B (zh) * 2021-01-27 2021-04-23 中国工程物理研究院流体物理研究所 一种新型液晶偏振调制器及其探测方法
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KR20180003788A (ko) 2016-07-01 2018-01-10 박준배 듀얼 모니터를 갖는 폴더폰
KR20180003783A (ko) 2016-07-01 2018-01-10 주식회사 아이에스앤로드테크 밤샘주차 단속 시스템 및 이를 이용한 방법
KR20180003784A (ko) 2016-07-01 2018-01-10 현대자동차주식회사 차량 및 그 제어방법
KR20180003787A (ko) 2016-07-01 2018-01-10 김광민 무(無)타카 펀치조립형 광고프레임 형성장치 및 방법
KR20180003785A (ko) 2016-07-01 2018-01-10 대우조선해양 주식회사 통합형 igg/gcu 시스템 및 그의 증발가스 처리 방법

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* Cited by examiner, † Cited by third party
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JP2020052276A (ja) * 2018-09-27 2020-04-02 大日本印刷株式会社 意匠材
JP7187937B2 (ja) 2018-09-27 2022-12-13 大日本印刷株式会社 意匠材
JP2022546819A (ja) * 2019-10-10 2022-11-09 エルジー・ケム・リミテッド 光変調デバイス
JP7283022B2 (ja) 2019-10-10 2023-05-30 エルジー・ケム・リミテッド 光変調デバイス
JP2022545386A (ja) * 2019-10-25 2022-10-27 エルジー・ケム・リミテッド 光変調デバイス
JP7443659B2 (ja) 2019-10-25 2024-03-06 エルジー・ケム・リミテッド 光変調デバイス

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